Process for selective methylation of phenols

ABSTRACT

Phenols represented by the formula   WHEREIN R1, R2, R3 and R4 represent individually a hydrogen atom or a methyl, ethyl, isopropyl, tert-butyl or a like saturated aliphatic hydrocarbon group, are selectively methylated in orthoposition by reacting the phenols with methanol in a gas phase at an elevated temperature using as a catalyst (1) (a) cerium oxide or a mixed oxide of rare earth elements composed mainly of cerium oxide; (2) a mixed oxide comprising said (a) in combination with (b) at least one oxide selected from the group consisting of titanium oxide, tin oxide, antimony oxide and bismuth oxide; (3) a mixed oxide comprising said (a) in combination with magnesium oxide; or (4) said (a) and (b) in combination with magnesium oxide.

Tasaka et al.

PROCESS FOR SELECTIVE METHYLATION OF PHENOLS Inventors: Akira Tasaka, Ibaragi-shi; Akira Morii, Takatsuki-shi; Yousuke Matoba, Osaka, all of Japan Sumitomo Chemical Company, Ltd., Osaka, Japan Filed: Sept. 29, 1969 Appl. No.: 861,989

Assignee:

Foreign Application Priority Data Oct. 5, 1968 Japan 43-72729 Oct. 7, 1968 Japan 43-73024 Oct. 31, 1968 Japan 43-79810 References Cited UNITED STATES PATENTS 10/1966 Hamilton et al. 260/624 C X 7/1967 Leston 260/624 C 10/1967 Froitzheim et al 260/621 R 5/1969 Hamilton 260/621 R X Primary Examiner-Leon Zitver Assistant ExaminerN0rman Morgenstern Attorney, Agent, or Firm--Stevens, Davis, Miller and Mosher [57] ABSTRACT Phenols represented by the formula wherein R R R and R represent individually a hydrogen atom or a methyl, ethyl, isopropyl, tert-butyl or a like saturated aliphatic hydrocarbon group, are selectively methylated in ortho-position by reacting the phenols with methanol in a gas phase at an elevated temperature using as a catalyst (1) (a) cerium oxide or a mixed oxide of rare earth elements composed mainly of cerium oxide; (2) a mixed oxide comprising said (a) in combination with (b) at least one oxide selected from the group consisting of titanium oxide, tin oxide, antimony oxide and bismuth oxide; (3) a mixed oxide comprising said (a) in combination with magnesium oxide; or (4) said (a) and (b) in combination with magnesium oxide.

21 Claims, No Drawings 14s Dec. 31, 1974 PROCESS FOR SELECTIVE METHYLATION OF PHENOLS This invention relates to a process for the methylation in ortho-position of phenols having at least one hydrogen atom in the ortho-position.

More particularly, the invention pertains to a process for the selective methylation in ortho-position of phenols represented by the formula wherein R R R and R represent individually a hydrogen atom or a saturated aliphatic hydrocarbon group, having l6 carbon atoms, e.g., a methyl, ethyl, isopropyl, tert-butyl or the like, which .process comprises reacting the phenols with methanol in a gas phase at an elevated temperature in the presence of a catalyst, characterized in that the catalyst is (1) (a) cerium oxide or a mixed oxide of rare earth elements containing as the prinicpal active ingredient cerium oxide; (2) a mixed oxide'comprising said- (a) in combination with (b) at least-one oxide selected from the group consisting of titanium oxide, tin oxide, antimony oxide and bismuth oxide; (3 )a mixed oxide comprising said (a) in combination with magnesium oxide; or (4) a mixed oxide comprising said.(a) and (b) in combination with magnesium oxide.

The process, in which a phenol having at least one ortho-position hydrogen atom, i.e. phenol, o-, mor P- cresol, 2,4-xylenol or the like, is methylated with methanol or dimethyl ether in a gas phase at an elevated temperature using a metal oxide as a catalyst thereby methylating the ortho-position of said phenol, is well known. For example, British Pat. No. 717,588 discloses a process, in which o-cresol is reacted with methanol in a gas phase at 300-450C., in the presence of an oxide of aluminum, thorium, zirconium, zinc, iron, manganese, calcium or barium, thereby obtaining 2,6-xylenol. According to said process, the yield of 2,6-xylenol per reacted o-cresol is 4476%,'and mand p-cresols are formed as by-products. In said process, however, the selectivity of methylating the ortho-position of phenol is not sufficient. Particularly, by-products similar in boiling point to the desired product are formed and difficulties are encountered in the separation and purification of the desired product.

Further, U.S. Pat. No. 3,446,856 teaches a process in which phenol, o-cresol or the like is reacted with methanol in a gas phase at 475-600C., in the presence of magnesium oxide as catalyst. When phenol is methylated according to said process, the sum of yields of ocresol and 2,6-xylenol per reacted phenol is 78-96%, and small amounts of anisole and 2,4,6,- trimethylphenol are formed as by-products. In said process, the selectivity of ortho-methylation is relatively favorable. However, the catalyst employed in said process requires an induction period of several hours be fore it becomes high in activity, and after a comparatively short period is lowered in activity so that regeneration thereof becomes necessary.

An object of the present invention is to provide a process for methylating the ortho-position of a phenol by reacting the phenol with methanol in a gas phase at an elevated temperature in the presence of a catalyst capable of giving suc'h advantages that:

1. only ortho-methylation proceeds with high selectivity per phenol and few by-products are formed, and

2. the conversion of phenol is high, and the catalyst is high in activity and is'not deteriorated in activity even when used for a long period of time.

Other objects will become apparent from the following description.

In order to accomplish the above-mentioned objects, the present inventors made repeated studies on a large number of oxide catalysts. As the result, the inventors found that cerium oxide; a mixed oxide of rare earth elements composed mainly of cerium oxide; and a mix-' ture thereof with magnesium oxide are excellent catalysts free from such drawbacks as mentioned above. The inventors further advanced the studies to find that when titanium oxide, tin oxide, antimony oxide or bismuth oxide is added to' the above-mentioned catalyst components, the efficiencies of the catalysts are further enhanced in the following points:

l. Useless decomposition of methanol is inhibited and selectivity ofthe desired product per mole of methanol is increased.

2. Conversion of phenol is enhanced and per-pass yield of ortho-methylation product is increased.

3. In the case of a phenol having hydrogen atoms in 2 ortho-positions, an ortho-dimethyl body is produced in a larger amount.

These properties are not only advantageous from the economical standpoint but also are markedly useful particularly when it is desired to obtain an orthodimethyl bodyjThe catalyst employed in the present invention contains, as an essential component, cerium oxide or a mixed oxide of rare earth'elements containing as the principal active ingredient cerium oxide; as

a first optional component(s), at least one member se-.

lected from the group consisting of titanium oxide, tin oxide, antimony oxide and bismuth oxide; and as a second optional component, magnesium oxide. The mixed oxide of rare earth elements should contain at least about 3O%.CeO

The essential component of the present catalyst, i.e., cerium oxide or a mixed oxide of rare earth elements containing as the principal active ingredient cerium oxide, will be explained below.

The primary catalytic action is possessed by cerium oxide, but a mixed oxide of rare earth elements composed in large part of cerium oxide also displays substantially the same effect. Particularly when a mixture of rare earth elements obtained from such naturally occurring minerals as monazite and the like is used as the starting material, i.e. without separation, there is attained such economical advantage that the steps for separation of individual rare earth elements can be omitted. Generally, the average composition of a mixed oxide of rare earth elements obtained fro-tn such starting material as mentioned above is 30-60%of cerium oxide (CeO 20-30% of lanthanum oxide (T421 0 15-25% of neodymium oxide (Nd O 38% of praseodymium oxide (Pr O l3% of samarium oxide (Smzoa), and others, and the main component of the mixed oxide is cerium oxide.

The above-mentioned cerium oxide and mixed oxides of rare earth elements can be prepared according to such processes as mentioned below:

l. a process carried out by adding caustic alkali, ammonia or the like to an aqueous solution of a nitrate or chloride of cerium or of mixed rare earth elements to form a hydroxide or a basic salt and then calcining and thermally decomposing said hydroxide or basic salt.

2. a process carried out by thermally decomposing a nitrate, carbonate or oxalate of cerium or mixed rare earth elements.

The first optional component to be blended with said cerium oxide or mixed oxide of rare earth elements, i.e. titanium oxide, tin oxide, antimony oxide or bismuth oxide, can be prepareed according to such ordinary processes as mentioned below.

1. A process carried out by hydrolyzing titanium tetrachloride, stannic chloride or antimony trichloride and then calcining the resulting hydroxide.

2. A process carried out by thermally decomposing bismuth nitrate, antimony nitrate or the like.

Further, the second optional component, i.e. magnesium oxide, can be prepared by thermal decompositon or the like of magnesium hydroxide or basic magnesium carbonate.

The presence of magnesium oxide is not indispensable but brings about advantages in that said oxide improves the selectivity of ortho-methylation, facilitates the shaping of catalyst and is usable as an economical diluent.

The above-mentioned components may be mixed together according 'to various processes. If possible, however, it is desirable for the preparation of a catalyst homogeneous. in composition that the components are mixed at the initial stage of catalyst preparation and then the mixture is subjected to thermal decomposition and the like treatment. Preferably, there is adopted a process carried out by adding an alkali such as ammonia or the like to a mixed aqueous solution of soluble salts of individual components to prepare a coprecipitate of hydroxides of the components; a process carried out by mechanically mixing separatelyprepared hydroxides of the components; or a process carried out by mechanically mixing a nitrate of one component(s) with a hydroxide of the other component(s). The resulting mixtures are calcined to obtain the desired mixed oxides.

The proportions of individual components in the mixed oxide can be selected from such a range that the weight ratio of (l) cerium oxide or a mixed oxide of rare earth elements: (2) titanium oxide, tin oxide, antimony oxide or bismuth oxide: (3) magnesium oxide is l:l.0:0 5.

The calcining temperature of the mixture is preferably 300900C., particularly perferably 500700C., and the calcination is desirably effected in an air current atmosphere.

A catalyst prepared by effecting the calcination in air is in a highly oxidized state. When used in the reaction, however, said catalyst is present in an oxidized state of a relatively low degree because it is in a reducing atmosphere. Therefore, even when catalysts are somewhat different in their oxidized state at the time of preparation, they are substantially the same in efficiency. It is, however, not desirable to adopt such calcining conditions that a part of the catalyst components deposit in .form of metal.

For industrial purposes, the aforesaid mixed oxides may be incorporated with more or less amounts of water, binders, lubricants, powdery carriers and the like and then shaped to be used as catalysts in the form of tablets, or they may be supported on a relatively inert carrier such as silica gel, calcined alumina, fire brick or diatomaceous earth to be used as supported catalysts.

The catalysts of the present invention are stable in activity over a long period of time. If, however, the catalysts have been lowered in activity due to operational errors or the like, the feeding of starting material is discontinued and air or steam is introduced at the reaction temperature for 2-24 hours, whereby the catalysts are completely regenerated.

Phenols capable of being methylated in accordance with the present invention are those represented by the formula (l)II wherein R R R and R represent individually a hydrogen atom or a saturated aliphatic hydrocarbon group, having 1-6 carbon atoms, e.g. a methyl, ethyl, isopropyl, tert-butyl or the like. Typical examples of such phenols include phenol itself, o-cresol, m-cresol, p-cresol, xylenols (excluding 2,6-xylenol), o-

ethylphenol, o-tert-butylphenol and p-tert-butylphenol.

Ortho-methylation products of these phenols contain o-cresol, 2,6-xylenol, 2,6-dimethyl-4-tert-butylphenol. etc., most of which are industrially important compounds as starting materials for polyphenylene oxide resins and bisphenols and intermediary starting materials for agricultural chemicals and medicines.

Reaction conditions to be employed in practicing the reaction by use of the present catalysts may be modified variously but can be summarized as follows:

The molar ratio of methanol to phenol to be adopted in the present invention is preferably within the range of from about I to 8. For the methylation of only one ortho-position, the adoption of a relatively low molar ratio (2-4) is preferable, and for the methylation of 2 ortho-positions, the adoption of a high molar ratio (4-7) is preferable. In some cases, the reaction gas may be diluted with a gas, which is not directly concerned with the reaction, e.g. nitrogen, steam or the like.

The reaction temperature varies depending on the activity of the catalyst employed, but is preferably 300600C., particularly preferably 40050C. At below 400C., the conversion of phenol is low, while at above 500C., compounds methylated in other positions than the ortho-position are by-produced in large amounts and useless decomposition ofmethanol frequently occurs.

The reaction pressure is from 0.5 to 20 atm. (absolute pressure). The reaction effectively proceeds even at atmospheric pressure, but it is also possible to conduct the reaction under a pressure of 2-10 atm. in order to enhance the efficiency of the reactor employed.

The feed rate of starting material per catalyst varies depending on other reaction conditions, but is preferably in the range of 10 to 200 mol/hr. per 1. of catalyst and is 224-4480 hr. when calculated to a gas space velocity.

The type of reactor employed may be any of the fixed bed or fluidized bed type. In the present reaction, however, the extent of reaction heat generated is relatively low and the regeneration of catalyst is scarcely required. It is therefore sufficient to adopt a fixed bed type reactor which is simple in operation.

The preferable material for constituting the reactor is stainless steel.

The reaction products which have been discharged from the reactor are cooled and collected and then unreacted methanol and unreacted phenols are removed by distillation, whereby the desired product can be obtained. In this case, the amounts of products, which have been methylated in other positions than orthopositions, are markedly small and therefore the purifi cation of the desired product can be simplified to a great extent. This is one of the characteristics of the present process.

When the present catalyst is used, it is relatively easy to obtain an ortho-dimethyl body from a phenol having 2 hydrogen atoms in the ortho-positions. Particularly when it is desired to obtain the ortho-dimethyl body alone, this can be easily done by recycling to the reactor a mono-methyl body, which is a reaction intermediate, together with the starting phenol.

The present invention will be illustrated below with reference to examples. However, it is not intended to limit the present invention. In the examples, there are employed expressions defined by the following equatrons:

Amount of fed methanol (moi/hr.)

Feed molar who 2 Amount of fed phenol (moi/hr.)

Phenol conversion (percent) Amount of fed phenol-Amount of unreaeted (moi/hr.) phenol (moi/hr.)

Amount of fed phenol (mol/hr.)

Phenol-based yield (percent) Amount of desired product (mol/hr.) Amount of fed phenol (moi/hr.)

Phenol-based selectivity (percent) Amount of desired product M (mol/hr.) Amount of Amount of fed phenol unreacted (moi/hr.) phenol (moi/hr.)

Methrtnol-lmsed selectivity (percent) Amount of methanol used in desired product (moi/hr.) Amount of fed Amount of unreaeted methanol (moi/hr.) methanol (mol/hr.)

R 9 Mixedoxide of rare earth elements.

EXAMPLE 1 quently, the precipitate was dried in air at 1 10C. and was then calcined in air at 500C. for 3 hours to obtain 49 g. of a yellowish brown cerium oxide catalyst. This catalyst was ground to 816 mesh and was subjected to a catalyst activity test.

(Catalyst Activity Test) A definite volume (10-20 cc.) of the catalyst ground to the aforesaid size was charged into a stainless steel reaction tube of 18 mm. in inner diameter and 600 mm. in length. On the catalyst layer were charged quartz pieces to be used as vaporizer. The reaction tube was heated with an electric furnace, and the reaction temperature was measured by measuring with a thermocouple the temperature at the central portion of the catalyst layer. Starting phenol and methanol were mixed and dissolved together in a given molar ratio and the solution was fed to the reaction tube at a given flow rate by means of a pump. The reaction products were collected in an air-cooled trap and a low temperature trap (78C.), and unreacted phenol and the'products were quantitatively analyzed according to gas chromatography using a 4.00 m. column of Silicon DC 550.(Reaction Conditions and Results); I

Shown in Table l-l.

EXAMPLE 2 (Catalyst) Same as in Example 1. (Reaction Conditions and Results):

Shown in Table 1-2.

From the results, it is seen that the catalyst activity scarcely changed over a long period of time from the initial stage of the reaction.

EXAMPLE 3 (Preparation of Catalyst) g. of a commercially available mixed rare earth metal (Misch metal; analysis values=48% Ce, 22% La, 19% Nd, 6% Pr, 2% Sm and 2% others) was carefully dissolved in 1000 g. of a 25% aqueous nitric acid solution. The solution was charged with 2 l of water and was heated to 50C. into this solution was added dropwise with stirring 1050 cc. of a 28% aqueous ammonia solution. After aging the mixed solution for 1 hour, a pale yellow precipitate formed was separated by centrifuge and was thoroughly washed with distilled water. Thereafter, the precipitate was dried at 120C. and was then calcined in air at 500C. for 3 hours to obtain g. of a black brown mixed oxide of rare earth elements. The thus obtained catalyst was ground to 8-16 mesh and was subjected to the same activity test as in Example 1.

(Reaction Conditions and Results) Shown in Table l-3. From the results, it is seen that the catalyst prepared in the above manner is somewhat higher in activity than a catalyst prepared by using cerium oxide alone.

EXAMPLE 4 (Preparation of Catalyst) 38 g. of ammonium ceric nitrate and 20 g. of didymium oxide (a mixed oxide of rare earth elements excluding cerium oxide) were dissolved in a large amount of a 20% aqueous nitric acid solution. To this solution was added with stirring at 50C. a 28% aqueous ammonia solution until the pH of the liquid became 10. After aging the liquid for 1 hour, a mixed hydroxide precipi- EXAMPLES 5 and 6 Catalysts comprising individually lanthanum oxide and neodymium oxide alone, which had been prepared by the calcination of hydroxides according to the same process as in any of Examples 1 to 4, were subjected to test in activity in the methylation of phenol to obtain the results as shown in Tables l-5 and 6.

Shown in Table 2-8. From the results, it is seen that the catalyst activity scarcely changed over a long period of time from the initial stage of the reaction.

EXAMPLE 9 (Preparation of Catalyst) 36 g. of ammonium ceric nitrate and 64 g. of magnesium nitrate were dissolved in 1 l of water. Into this solution was added dropwise with stirring at 50C. 190 cc. of a 28% aqueous ammonia solution. Thereafter, the same operation as Example 7 was effected to obtain 43 g. of a pale brown 50% CeO 50% MgO catalyst. (Reaction Conditions and Results) Shown in Table 2-9. The ortho-methylation selectivity of this catalyst was 97% on an average.

EXAMPLES 10 and 11 A commercially available mixed rare earth metal (48% Ce, 22% La, 19% Nd, 6% Pr and 2% Sm) was dissolved in dilute nitric acid. This liquid was mixed in var- Table l.

Methylation of Phenol with Methanol (Stainless steel reaction tube of 18 mm. in inner diameter; pressure atmospheric).

Reaction conditions Phenol-based yields of products (mol '7!) Reac- Gas Phenol o-Crcsol. Ex. Vol- Feed tien space Elapcon- 2.6- 2.4- Tri- 2.6-

11ml: No. Catalyst (cc.) molar temp. velosed ver- Aniom,p- Xyle- Xylemethyl Xylenol ratio (C) city time sion sole Cresol Cresol nol nol phenol select- (hr.) 1%) ivilHr/U 1 CeO l8 6 403 1.080 12 29.6 1.4 26.2 0 2.0 0 0 95.4 do. do. 447 do. 13 58.3 2.6 40.5 0.3 14.0 0.8 0 93.4 do. do. 488 do. 14 59.5 2.6 41.6 0.3 13.2 0 1.4 92.1 2 (e0 18 3 449 900 1 41.8 1.11 34.3 0.1 4.7 0.5 0.4 93.3 do. do. do. do. 11 39.1 1.4 33.2 0.2 4.0 0.3 0 95.1 do. do. do. do. 90 39.5 1.0 33.8 0.1 4.1 0.5 0 95.6 3 R 0 12 6 420 1.100 1 58.4 3.5 42.2 0 11.7 0.7 0.3 92.3 (CeO, do. do. 449 do. 2 74.8 4.1 37.2 0 31.4 1.0 1.0 91.7 48%) do. do. 469 do. 3 81.2 3.8 33.7 0 40.0 0.8 2.9 90.8 4 R 0 16.5 6 429 1.200 1.5 33.1 1.7 29.8 0.1 1.5 0 0 94.7 (CeO do. do. 453 do. 2.5 73.4 3.3 54.1 0.1 14.0 1.9 0 92.9 31%) do. do. 473 do. 3.5 90.9 4.1 45.0 0 39.2 1.5 1.] 92.7 5 Lat- 0; 20 6 '493 1.000 3 22.2 7.3 13.7 0.3 0.9 0 0 65.8 do. do. 532 do. 4 76.2 15.0 46.6 0 11.3 3.3 0 76.1 6 Nd-,O 18.5 6 497 1.050 3 16.0 4.8 9.5 1.7 0 0 0 59.3

EXAMPLE 7 ious proportions with an aqueous magnesium nitrate (Pre aration of Catal St) solution, and was then charged with an aqueous ammoy nia solution until the pH of the liquid became 10.

43 g. of ammonium ceric nitrate [Ce(NO ).,-2(NH- NO )'2H O] and 306 g. of magnesium .nitrate [Mg(NO '6H O] were dissolved in 2.5 10f water. Into this solution was addeddropwise with stirring at 50C. 700 cc. ofa 28% aqueous ammonia solution. A precipitate of mixed hydroxide formed was separated by centrifuge, was washed, was dried at 1 10C. and was then calcined in air at 500C. for 3 hours to obtain a pale brown 20% CeO 80% MgO catalyst. The thus obtained catalyst was ground to 8-16 mesh and was then EXAMPLE 8 (Catalyst) Same as in Example 7. (Reaction Conditions and Results) Mixed hydroxides obtained in the above manner were thermally decomposed to prepare rare earth element oxide-magnesium oxide catalysts containing individually 50% and by weight of mixed oxide of rare earth elements. (Reaction Conditions and Results) Shown in Table 2-10 and 11.

COMPARATIVE EXAMPLE Basic magnesium carbonate was thermally decomposed to prepare a magnesium oxide catalyst. This catalyst was used under the same reaction conditions as in the preceding Examples to obtain the results set forth in the last lines of Table 2. From the results, it is seen that when magnesium oxide is used alone, the resulting catalyst is low in activity and less selective in orthomethylation at temperatures within the range of about 450 to 500C.

Table' 2 Methylation of Phenol with Methanol (Stainless steel reaction tube of 18 mm. in inner diameter; pressure atmospheric) I Phenol based yields of products o-Cresol. Reaction conditions (mol /1) 2.6-

Reac- Gas Elap- Phenol Ex. Vol. 1 Feed tion space sed con- 2.6' 2,4- Tri Xylcnol No. Catalyst (cc) molar temp. velotime ver- Ani om.p- Xyle- Xylemethyl selecratio (C) city (hr.) sion sole Cresol Cresol nol nol phenol tivity lhr") ("/l) (/1) 7 20% CeO 20 6 453 1.000 10 36. 0.8 32.6 2.5 0.4 0 96.1 80% MgO do. do. 493 do. 8 81.1 2.4 53.0 0.2 23.5 0.9 1.3 94.3

8 20% CeO- 20 6 454 1.000 1 36.1 1.0 32.3 0 2.8 0 0 97.2 80% MgO do. do. 453 do. 36.5 0.8 32.6 0 2.5 0.4 0 961 do. do. 453 do. 85 35.9 0.7 31.8 0 2.2 0.3 0 94.8

9 50% CeO 6 404 1000 l 23.0 0.5 21.8 0 0.7 i 0 (1 94.8 50% MgO do. do. 449 do. 2 80.8 1.2 58.4 0 19.2 1.2 0 98.2

do. do. 485 do. 3 83.7 2.0 55.6 0 26.1 0 0 97.6 g

10 5071 R 0 20 6 419 1.000 0.5 20.4 1.2 18.2 "0.1 0.9 0 0 93.6 50% MgO do. do. 443 do. 1 41.9 2.0 37.0 0.1 -2.8 0 0 94.9 do. do. 466 1.050 2 69.4 3.1 55.1 0 9.8 0.9 0.3 93.6

ll 80% R- O 20 6 449' 1.000 2 70.4 3.3 38.1 0.1 27.0 0.9 0.8 92.5

20% MgO ompara- MgO 20 6 460 1.001 9 18.6 0.3 15.9 1.4 0.5 0.5 0 87.6 tive do. do. 503 do. 8 48.8 0.4 40.2 1.7 5.3 1.6 1.6 89.6 Ex.

30 EXAMPLE 12 Example 12 to prepare a 10% Sb O 90% R 0 cata- (Preparation of Catalyst) 50 g. of a commercially available mixed rare earth metal (comprising 50% Ce, La, 18% Nd, 6% Pr and 1% Sm) was dissolved in 500 g. of nitric acid. This solution was mixed with a solution formed by hydrolyzing 35.5 g. of titanium tetrachloride with about 1000 cc. of water. Into this mixed solution was added dropwise at 50C. 700 cc. of a 28% aqueous ammonia solution. After aging the mixed solution at 50C. for 1 hour, a mixed hydroxide precipitate formed was separated by centrifuge, was thoroughly washed with a dilute aqueous ammonia solution, was dried in air at 120C. and was then calcined in air at 500C. for 3 hours to obtain 52.2 g. of a brown 20% Ti 0 80% R 0 catalyst. (Reaction Conditions and Results):

Shown in Table 3-12.

EXAMPLE 13 (Preparation of Catalyst) 50 g. of the mixed rare earth metal of Example 12 was dissolved in 500 g. of 30% nitric acid. This solution was mixed with a solution formed by hydrolyzing 1 1.8 g. of stannic chloride with about 500 cc. of water. Into the mixed solution was gradually added dropwise with stirring at 50C. 700 cc. ofa 28% aqueous ammonia solyst. (Reaction Conditions and Results) Shown in Table 3-14.

EXAMPLE 15 EXAMPLE 16 135 g. of ammonium ceric nitrate [Ce(NO -2NH- NO -41-1 O] was dissolved in 500 cc. of water. This solution was mixed with a solution formed by hydrolyzing lution. After aging the mixed liquid for 1 hour, a mixed EXAMPLE 14 The mixed rare earth metal of Example 12 and antimony trichloride were treated in the same manner as in 5.6 g. of stannic chloride (SnC1 with 500 cc. of water. Thereafter, the mixed solution was treated in the same manner as in Example 13 to obtain a brown 5% SnO CeO catalyst. (Reaction Condition and Results) Shown in Table 3 -16.

EXAMPLE 17 67.8 g. of ammonium ceric nitrate and 127 g. of magnesium nitrate [Mg(NO 61-1 O] 'were dissolved in about 1500 cc. of water. This solution was mixed with a solution formed by hydrolyzing 23.7 g. of titanium tetrachloride with about 500 cc. of water. Into the mixed solution was added dropwise with stirring at EXAMPLES 18 22 o-Cresol was methylated with methanol under the reaction conditions set forth in Table 4 in the presence Table 3 of the mixed oxide catalysts employed in Example 3, 9, 10, 13 and 17, respectively, to obtain the results shown in Table 4.

EXAMPLES 23-25 m-Cresol was methylated with methanol under the reaction conditions set forth in Table 5 in the presence of the mixed oxide catalysts employed in Examples 3,

9, and 13, respectively, to obtain the results shown in Table 5.

Methylation of Phenol with Methanol (Stainless steel reaction tube of 18 mm.

in inner diameter; pressure atmospheric) Ph 1- 14 th 1- R d e Phenol baeodields of product s: g gno E Reec- Gas E15 Phenol o-croeol,

Volume Feed tion space F conver- 2 2 2 p111; Catalys (00.) mole:- tempervelo- :g e105 Aniorn,px5111. methyl gal- 223i Kyieno} ra'lzio eft tge) ((22:3 (mu) (,4) sale Creeol Creeol nol nol phenol 333027;)-

13 10% Sn0 20 e 433 970 1 94.7 0.3 35.8 0 54.3 1.0 4.9 93.6 38.4 9095 R 0 454 2 97.6 0.7 24.4 0 69.3 1.6 3.9 93.8 38.7

15 B1 0 20 6 424 970 1 78.8 0.5 41.5 0 31.8 2.2 1.8 94.3 33.5 80% R 0 441 2 90.3 0.4 35.5 o 48.1 1.2 2.9 94.9 27.7

17 2% T10 20 6 465 850 6 66.2 3.9 47.4 1.4 10.1 2.7 0.7 86.9 64.6 C90 508 900 7 98.1 3.7 24.7 0 51.3 5.4 13.0 77.5 32.4 40% x Table 4.

Methylation of o-Cresol with Methanol (Stainless steel reactiontube of 18 mm. in inner diameter: pressure atmospheric) Reaction Conditions o-Cresol-based yields of Products ("/11 o-Cresol Vol- Reae- Gas o-Cresol I based Ex. ume Feed tion space Elapcon- 2.6- 2.4- Tri- 2,6- No. Catalyst (cc) molar temp. velosed ver- Ani- Phem.p- Xyle- Xylemethyl- Xylenol ratio 1C) city time sion sole nol Crenol nol phenol selec- (hr") (hr.) sol tivity (7.)

18 R 0; 12 3 430 1,000 4 42.3 0 0.2 0 40.7 0.3 0.9 96.2 (CeO: do. do. 453 do. 5 53.9 0.2 0.4 0 51.0 0.2 1.8 94.7 487:) do. do. 475 do. 6 55.3 0.5 1.4 0 51.1 0.5 2.5 92.1 19 509i CeO- 20 3 422 850 4 37.0 0 0.1 0 36.4 0.1 0 99.5 5071 MgO do. do. 443 do. 5 51.4 0 0.3 0 48.5 0.2 0.7 97.7 do. do. 462 do. 6 54.6 0 1.1 0 46.5 0.2 0.8 96.1 20 V: R- .O 20 3 423 800 4 21.0 0.2 0.2 0 20.8 0 0 99.4 5071 MgO do. do. 454 do. 5 40.8 0.2 0.9 0 39.3 0.2 0.2 96.4 do. do. 470 do. 6 55.5 1.5 0 52.1 0.2 1.5 93.9 21 107: SnO- 20 6 411 960 4 31.4 0.3 0.2 0 29.9 0.9 1.2 95.4 907/ R 0 do. do. 435 do. 5 67.6 0.4 0.3 0 63.5 0.7 3.1 93.9 22 2071 T10. 20 6 420 850 8 21.8 0 0.4 0 20.0 1.1 0.3 93.7 4071 (00.- do. do. 451 do. 9 45.9 0 0.7 0 40.8 2.4 2.0 90.4 4071 MgO do. do. 485 800 10 77.2 0 0.5 0 64.3 2.9 9.5 83.9

Table 5 Methylation of m-Cresol with Methanol (Stainless steel reaction tube of 18 mm. in inner diameter; pressure atmospheric) Reaction conditions m-Cresol-based yields of products Ortho- Reaction Gas m-Cresol methylalion Example Catalyst Vol- Feed temperspace Elapsed conver- 2.3.6- product ume No. (cc.) molar ature velocity time sion 2.3- 2.5- Trimethylselectivity ratio (C.) (hr") (hr.) (7:) Xylenol Xylenol phenol ('4) (Coo- 41191) Table -Continued Methylation of m-Cresol with Methanol (Stainless steel reaction tube of IX mm. in inner diameter; pressure atmospheric) Reaction conditions t1\-(resol h;tsetl yields of products ()rtho A was Reaction Gas m-Crcsol methylation Example Catalyst Vol- Feed tcmperspace Elapsed conver- ".16 product ume No. tcc.) molar aturc velocity time sion 2.3- 2.5- Trimethyl selectivity ratio (C.) lhr) (hr.) ('71) Xylcnol Xylenol phenol (/1) 24 50% CeO 3 450 l.()()() 3 76.2 20.] 25.3 224 89.0

5071 MgO 10% SnO 20 3 425 960 7 54.2 l2.0 20.3 l8.7 94.2

EXAMPLES 26-28 comprising said (a) and magnesium oxide with the p-tert-Butylphenol was methylated with methanol 20 weight ratio of 11014-0 and a mixed Oxide under the reaction conditions set forth in Table 6 in the presence of the mixed oxide catalysts employed in Examples l, 9 and 13. respectively, to obtain the results shown in Table 6.

duced by calcination comprising (a), (b) and (c) magnesiumoxide, the weight-ratio of components (a) to (b) to (c) being l:0.0l-l.0:0.l-5.0.

2. A process according to claim 1 wherein R,, R R

Table 6.

Methylation of p-t-Butylphenol with Methanol Stainless steel reaction tube of 18 mm. in inner diameter; pressure atmospheric) Reaction conditions p-tcrtp-tert-Butylphenol-bascd Ortho- Reaction (ias Butylyields of products (4) methylation [:x. Catalyst Vol- Feed temperspace Elapsed phenol 2-Methyl-4- 2.6-Dimethylproduct ume No. tee.) molar ature velocity time conversion t-hutyl- 4-tcrt-hutylselectivity ratio (C.) (hr') (hr.) ('7!) phenol phenol (/r) 26 C00 18 g 6 450 1,000 3 62.5 40.1 15.9 89.6 27 50% C60 20 6 450 1.000 3 75. 61.0 l0.3 94.8

50% MgO 28 10% SnO; 20 6 450 L000 ll 82.3 50.2 28.0 95.0

What is claimed is: l. A process of methylation the the ortho-position of aphenol represented by the formula (IHI Rt- H a phenol represented by the formula wherein R R R and R represent individually a hydrogen atom or a saturated aliphatic hydrocarbon group having 1-6 carbon atoms, which comprises reacting the phenol with methanol in the gas phase at a temperature of from 300to 600C. under a pressure from 0.05 to 20 atms. absolute, in the presence ofa catalyst selected from the group consisting of l) a mixed oxide producedby. calcination comprising (a) cerium oxide or a-mixed oxide of rare earth elements containingat least 30 percent by weight of cerium oxide in combination with (b) at-least one oxide selected from the group consisting of titanium oxide, tin oxide, antimony oxide and bismuth oxide with the weight ratio of l:0.0l-l .0; (2) a-mixed oxide produced by calcination wherein R R R and R represent individually a hydrogen atom or a saturated aliphatic hydrocarbon group having 1-6 carbon atoms, which comprises reacting the phenol with methanol in the gas phase at a temperature of from 300 to600C. under a pressure from 0.5 to 20 atms. (absolute) in the presence ofa catalyst produced by calcination comprising (a) cerium oxide or a mixed oxide of rare earth elements containing at least 30 percent by weight of cerium oxide and (c) magnesium oxide, the weight ratio of components (a) to'(c) being l:0.l-5.0

4. A process of methylation in the ortho-position of a phenol represented by the formula wherein R,, R R and R, represent individually a hydrogen atom or a saturated aliphatic hydrocarbon group having 1-6 carbon atoms, which comprises reacting the phenol with methanol in the gas phase at a temperature of from 300 to 600C. under a pressure from 0.5 to 20 atms. (absolute) in the presence ofa catalyst produced by calcination comprising (a) cerium oxide or a mixed oxide of rare earth elements containing at least 30 percent by weight of cerium oxide and (b) at least one oxide selected from the group consisting of titanium oxide, tin oxide, and bismuth oxide, the weight ratio of components (a) to (b) being 1:0.0l-l .0.

5. A process of methylation in the ortho-position of a phenol represented by the formula wherein R R R and R, represent individually a hydrogen atom or saturated aliphatic hydrocarbon group having l-6 carbon atoms, which comprises reacting the phenol with methanol in the gas phase at a temperature of from 300 to 600C. under a pressure from 0.5 to 20 atms. (absolute) in the presence of a catalyst produced by calcination comprising (a) cerium oxide or a mixed oxide of rare earth elements containing at least +percent by weight of cerium oxide and (b) at least one oxide selected from the group consisting of titanium oxide, tin oxide, antimony oxide and bismuth oxide and (c) magnesium oxide, the weight ratio of components (a) to (b) to (c) being l:0.0ll.0:0.l5.0.

6. A process according to-claim 3, wherein the weight ratio of (a) the mixed oxide of rare earth elements to (c) magnesium oxide is l:0.ll.

7. A process according to claim 1, wherein the weight ratio of (a) the mixed oxide of rare earth elements to (b) at least one oxide selected from the group consisting of titanium oxide, tin oxide, antimony oxide and bismuth oxide to (c) magnesium oxide is 1:0.0l-lz0- .ll.0.

8. A process according to claim 1, wherein the phenol to be methylated is phenol and the product is composed mainly of o-cresol.

9. A process according to claim 1, wherein the phenol to be methylated is o-cresol and the product is composed mainly of 2,6-xylenol.

10. A process according to claim 1, wherein the phenol to be methylated is phenol and the product is composed of o-cresol and 2,6-xylenol.

11. A process according to claim 1, wherein the phenol to be methylated is a mixture of phenol and o-cresol and the product is a mixture of o-cresol and 2,6- xylenol.

12. A process according to claim 1, wherein the phenol to be methylated is m-cresol and the product is a mixture of 2,3-xylenol, '2,5-xylenol and 2,3,6- trimethylphenol.

13. A process according to claim 1, where R,, R R and R in the formula representing the phenol to be methylated are individually a hydrogen atom or a saturated aliphatic hydrocarbon group having l-4 carbon atoms.

14. A process according to claim 1, wherein the molar ratio of methanol to phenol is 111-8.

15. A process according to claim 18, wherein the ratio is l:26.

16. A process according to claim 1, wherein the temperature is 400-500C.

17. A process according to claim 1, wherein the pressure is ll0 atm. absolute.

18. A process according to claim 1, wherein the feed rate of the starting material is 10-200 mol/hr. per liter of the catalyst.

19. A process according to claim 1, wherein the catalyst is used in a fixed bed.

20. A process according to claim 1, wherein the catalystis used in a fluidized bed.

21. A process according to claim 1, wherein a monomethyl body as a reaction intermediate is recycled to the reaction system when the phenol to be methylated has hydrogen atoms in two ortho-positions and the product is a dimethyl-substituted compound having dimethyl groups in two ortho-positions. 

1. A PROCESS OF METHYLATION THE ORTHO-POSITION OF A PHENOL REPRESENTED BY THE FORMULA
 2. A process according to claim 1 wherein R1, R2, R3 and R4 represent individually hydrogen, methyl, ethyl, isopropyl or tert-butyl.
 3. A process of methylation in the ortho-position of a phenol represented by the formula
 4. A process of methylatiOn in the ortho-position of a phenol represented by the formula
 5. A process of methylation in the ortho-position of a phenol represented by the formula
 6. A process according to claim 3, wherein the weight ratio of (a) the mixed oxide of rare earth elements to (c) magnesium oxide is 1:0.1-1.
 7. A process according to claim 1, wherein the weight ratio of (a) the mixed oxide of rare earth elements to (b) at least one oxide selected from the group consisting of titanium oxide, tin oxide, antimony oxide and bismuth oxide to (c) magnesium oxide is 1:0.01-1:0.1-1.0.
 8. A process according to claim 1, wherein the phenol to be methylated is phenol and the product is composed mainly of o-cresol.
 9. A process according to claim 1, wherein the phenol to be methylated is o-cresol and the product is composed mainly of 2,6-xylenol.
 10. A process according to claim 1, wherein the phenol to be methylated is phenol and the product is composed of o-cresol and 2,6-xylenol.
 11. A process according to claim 1, wherein the phenol to be methylated is a mixture of phenol and o-cresol and the product is a mixture of o-cresol and 2,6-xylenol.
 12. A process according to claim 1, wherein the phenol to be methylated is m-cresol and the product is a mixture of 2,3-xylenol, 2,5-xylenol and 2,3,6-trimethylphenol.
 13. A process according to claim 1, where R1, R2, R3 and R4 in the formula representing the phenol to be methylated are individually a hydrogen atom or a saturated aliphatic hydrocarbon group having 1-4 carbon atoms.
 14. A process according to claim 1, wherein the molar ratio of methanol to phenol is 1:1-8.
 15. A process according to claim 18, wherein the ratio is 1:2-6.
 16. A process according to claim 1, wherein the temperature is 400*-500*C.
 17. A process according to claim 1, wherein the pressure is 1-10 atm. absolute.
 18. A process according to claim 1, wherein the feed rate of the starting material is 10-200 mol/hr. per liter of the catalyst.
 19. A process according to claim 1, wherein the catalyst is used in a fixed bed.
 20. A process according to claim 1, wherein the catalyst is used in a fluidized bed.
 21. A process according to claim 1, wherein a monomethyl body as a reaction intermediate is recycled to the reaction system when the phenol to be methylated has hydrogen atoms in two ortho-positions and the product is a dimethyl-substituted compound having dimethyl groups in two ortho-positions. 